US5892059A - Process for producing a rose oxide - Google Patents

Process for producing a rose oxide Download PDF

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US5892059A
US5892059A US08/966,185 US96618597A US5892059A US 5892059 A US5892059 A US 5892059A US 96618597 A US96618597 A US 96618597A US 5892059 A US5892059 A US 5892059A
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diol
acid
oct
mixture
dimethyl
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Wilhelm Pickenhagen
Dietmar Schatkowski
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Symrise AG
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Dragoco Gerberding and Co GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms

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  • the invention concerns an improved process for production of an isomer mixture of Z- and E-2- 2-Methyl-prop-1-en-1-yl-!-4-methyltetrahydropyran of the General Formula A, more commonly known under the name cis- and trans-rose oxide, which as a rule contains at least 80% of the natural Z-isomers (cis-rose oxide) which are valuable in the perfume industry.
  • This isomer mixture will hereafter also be referred to as "rose oxide of General Formula A"; this concept includes racemic as well as optically active isomer mixtures.
  • rose oxide includes in the framework of this application, besides the inventive isomer mixture ("rose oxide of General Formula A”) with as a rule at least 80% of the Z-isomer, also other mixtures of the Z- and E-isomers as well as the pure isomer and enantiomer.
  • the inventive process leads to good results, independent thereof, whether 3,7-dimethyl-oct-7-en-1,6-diol (3b) individually or in mixtures with 3,7-dimethyl-oct-5-en-1,7-diol (3a) is converted into rose oxide.
  • FIG. 1 shows a process which converts citronellol by photochemical sensitized singlet-oxygen-oxidation, whereby one obtains, depending upon selection of citronellols, beginning with (-)-citronellol the (-)-rose oxide, beginning with (+)-citronellol the (+)-rose oxide and beginning with racemic (+/-)-citronellol the mixture of the cis-/trans-isomer optically inactive rose oxide.
  • FIG. 2 shows the inventive process (with variants A, B, C, D) which makes possible the conversion of 3,7-dimethyl-oct-7-en-1,6-diol (3b) individually or in mixtures with 3,7-dimethyl-oct-5-en-1,7-diol (3a) into rose oxide (5a/b) Z-/E-2-(2-methyl-prop-1-en-1-yl)-4-methyl-tetrahydro-pyran!.
  • a rose oxide itself; this is mixed with the 3,7-dimethyl-oct-7-en-1,6-diol (3b) or the diol-mixture (3a+3b) before or during the inventive acid treatment and/or it forms itself during the acid treatment in situ from the 3,7-dimethyl-oct-5-en-1,7-diol (3a) which, in certain cases, is present.
  • a rose oxide particularly good yields for the conversion of the diol (3b) to rose oxide of the General Formula A are achieved.
  • an amount of the 3,7-dimethyl-oct-7-en-1,6-diol (3b), in certain cases mixed with the diol (3a), is mixed with an equal, larger or only slightly smaller amount of rose oxide.
  • Such a supplementation or addition of rose oxide in more than necessary catalytic amount leads frequently to particularly good yields.
  • the inventive process is carried out at elevated temperatures.
  • the reaction temperature during the acid treatment is at least for that time adjusted to the boiling point of the liquid phase; in the two phase liquid/liquid system it is adjusted to the boiling point of the lower boiling liquid phase.
  • diol-mixture (3a+3b) or the diol (3b) there can be employed for example sulfuric acid, phosphoric acid, and acid activated clay or Fuller's Earth, or a heteropolytungstic acid such as tungstate silicic acid or tungstate phosphoric acid may be employed.
  • inventive acid treatment is carried out in a two phase liquid/solid system by means of a carrier bound acid
  • a conventionally acid activated calcium montmorillonite such as MONTMORTILLONITE K10, MONTMORTILLONITE KSF, activated strongly acidic clay (FILTROL), activated natural calcium bentonite (KATALYSATOR KS, TONSIL OPTIMUM) and the like products available commercially.
  • FULLER acid activated calcium montmorillonite
  • FILTROL activated strongly acidic clay
  • KATALYSATOR KS, TONSIL OPTIMUM activated natural calcium bentonite
  • phase transfer catalysts for example methyltrioctylammonium chloride (ALIQUAT), tetrabutyl ammonium-chloride-bromide or hydrogen phosphate, for example in concentrations of 0.1 weight % to 10 weight %, preferably from 4-6 weight %, with respect to the amount of the employed diol mixture (3a+3b) or the diol (3b).
  • phase transfer catalysts as for example methyltrioctylammonium chloride (ALIQUAT), tetrabutyl ammonium-chloride-bromide or hydrogen phosphate, for example in concentrations of 0.1 weight % to 10 weight %, preferably from 4-6 weight %, with respect to the amount of the employed diol mixture (3a+3b) or the diol (3b).
  • aprotic solvent in particular pentane, hexane, heptane, cyclohexane, benzol, toluol or xylol as well as similar conventional carbohydrates and mixtures thereof can be employed.
  • Iso-rose oxide (B) characterizes itself by fatty-terpene, somewhat weedy or cabbage-like aspects. A presence in amounts of less than 2% in the cyclization product thus leads to a deterioration or detraction in the use of this composition as aromatic compound.
  • the inventive process herein comes to advantage, that one can transform the diol 3b both in mixture with as well also separate from diol 3a each according to selection of the reaction conditions under significant yield enhancement in only a single step into an at least 80% cis-rose oxide (5a).
  • the conversion or forming of the sensory undesirable iso-rose oxide (B) occurs in the subsequent carried out process-variants A, B, C, D (Examples 3-6) in the range of ⁇ 2%.
  • the Examples 1 and 2 concern preferred process steps for production of racemic citronellyl-hydroperoxide (2a/b) and racemic diol mixtures (3a/b).
  • Examples 3-6 each concern respectively one inventive production of racemic cis/trans-rose oxide (5a+5b) from the diol mixture 3a/b produced in accordance with Example 2.
  • Example 7 concerns the production of a mixture of optically active (-)-3,7-dimethyl-oct-5-en-1,7-diol and (-)-3,7-dimethyl-oct-7-en-1,6-diol;
  • Example 8 concerns the production according to the invention of (-)-cis/trans-rose oxide beginning with this mixture.
  • Examples 9 and 10 concern the corresponding inventive production of a mixture of an optically active (+)-3,7-dimethyl-oct-5-en-1, 7-diol and (+)-3,7-dimethyl-oct-7-en-1,6-diol as well as the production of (+)-cis/trans-rose oxide produced in accordance with the invention from this mixture.
  • Example 11 concerns the production of (undesirable) diol 3,7-dimethyl-oct-7-en-1,6-diol (3b).
  • Example 12 concerns a non-inventive (comparative) example for production of racemic cis/trans-rose oxide from the undesirable diol (3b) according to Example 11; the Examples 13 and 14 are, in comparison, preferred inventive Examples for production of the racemic cis/trans-rose oxide from the unmixed diol (3b) wherein the inventive yield according to Example 14 is significantly higher than that according to Example 13.
  • MS (70 eV):m/e (%) 154 (16, M.sup. ⁇ ), 139 (100), 85 (13), 83 (28), 69 (63), 67 (11), 55 (28), 39 (15).
  • MS (70 ev):m/e (%) 154 (11, M + ), 139 (100), 85 (11), 83 (26), 69 (63), 67 (11), 55 (29), 39 (15).
  • MS (70 eV): m/e (%) 154 (35, M + ), 139 (100), 83 (22), 71 (50), 69 (61), 67 (23), 55 (64), 41 (79).
  • MS (70 eV): m/e (%) 154 (37, M + ), 139 (100), 83 (23), 71 (49), 69 (68), 67 (25), 55 (62), 41 (80).
  • thermometer and return flow cooler 300 g toluol, 50 g 50% sulfuric acid, 1 g Aliquat® R 336 and 50 g (0.27 mol) diol-mixture 3a/b (from Example 2) were added with mixing over 15 minutes with return circulation, cooled to room temperature, the organic phase separated, washed to neutral with sodium solution and water, dried over sodium sulfate and the solvent distilled off under reduced pressure.
  • MS (70 eV): m/e (%) 154 (10.M + ), 139 (100), 85 (11), 83 (24), 69 (58), 67 (11), 55 (22), 41 (23), 39 (14).
  • MS (70 eV): M/E (%) 154 (35.M + ), 139 (100), 83 (21), 71 (49), 69 (60), 67 (23), 55 (64), 41 (78).
  • MS (70 eV): m/e (%) 154 (37.M + ), 139 (100), 83 (22), 71 (50), 69 (68), 67 (24), 55 (63), 41 (80).
  • MS (70 eV): m/e (%) 154 (12.M + ), 139 (100), 85 (10), 83 (23), 69 (55), 67 (10), 55 (21), 41 (21), 39 (13).
  • MS (70 eV): m/e (%) 154 (35.M + ), 139 (100), 83 (22), 71 (50), 69 (61), 67 (23), 55 (64), 41 (79).
  • MS (70 eV): m/e (%) 154 (10.M + ), 139 (100), 83 (23), 71 (49), 69 (68), 67 (25), 55 (62), 41 (80).
  • thermometer and return flow cooler 100 g toluol, 0.5 g tetrabutyl ammonium hydrogen sulfate, 25 g H 3 PO 4 85% and 60 g (0.32 mol) diol-mixture (from Example 2) were added with mixing over a period of 10 minutes with return flow, cooled to room temperature, the organic phase separated off, washed neutral with soda solution, dried over sodium sulfate and the solvent distilled off under reduced pressure.
  • MS (70 eV): m/e (%) 154 (14.M + ), 139 (100), 85 (11), 83 (27), 69 (59), 67 (10), 55 (26), 41 (22), 39 (14).
  • MS (70 eV): m/e (%) 154 (11.M + ), 139 (100), 85 (10), 83 (25), 69 (58), 67 (10), 55 (26), 41 (19), 39 (13).
  • MS (70 eV): M/E (%) 154 (36.M + ), 139 (100), 83 (24), 71 (53), 69 (60), 67 (25), 55 (67), 41 (77).
  • MS (70 eV): m/e (%) 154 (36.M + ), 139 (100), 83 (21), 71 (51), 69 (68), 67 (25), 55 (60), 41 (78).
  • (+)-cis-Rose oxide 90.1%
  • GC/MS-Data correspond to the natural isolate.
  • Example 2 Beginning with the mixture described in Example 1 for production of citronellyl-hydroperoxide (2a/b), which after reduction under the conditions set forth in Example 2 were converted to a mixture of the racemic diol 3a/b, one obtains by acidic cyclization according to the method described in L. -F. Tietze, Th. Eicher a mixture of the two cis/trans-Rose oxide (5a/b) as well as the not converted 3,7-dimethyl-oct-7-en-1,6-diol (3b).
  • thermometer and return flow cooler and water separator 15.0 g (0.078 mol) 3,7-dimethyl-oct-7-en-1,6-diol (3b) (from Example 11), 500 ml cyclohexane, 1 g Filtrol® and 8.9 g (0.078 mol) 4-methoxy-2-methyl-2-pentene (as an example of an allylether) were added in with mixing over a time of 9 hours. During this time a total of 0.7 ml H 2 O were separated off.
  • Examples according Examples 11-14 were carried out with a likewise appropriate optically active adduct species (Citronellol, Citronellyl-Hydroperoxide, diol 3b). There were produced respectively analogous results.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Pyrane Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Fats And Perfumes (AREA)
US08/966,185 1996-11-08 1997-11-07 Process for producing a rose oxide Expired - Fee Related US5892059A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19645922.2 1996-11-08
DE19645922A DE19645922A1 (de) 1996-11-08 1996-11-08 Verfahren zur Herstellung von Rosenoxid

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US (1) US5892059A (enExample)
EP (1) EP0842926B1 (enExample)
JP (1) JPH10168075A (enExample)
DE (2) DE19645922A1 (enExample)
ES (1) ES2170910T3 (enExample)
IL (1) IL122108A (enExample)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003087387A1 (en) * 2002-04-08 2003-10-23 Council Of Scientific And Industrial Research Chemo-enzymatic synthesis of optically enriched rose-oxides
WO2006070383A1 (en) * 2004-12-27 2006-07-06 Council Of Scientific And Industrial Research Process for the preparation of nerol oxide
US20080187159A1 (en) * 2006-10-23 2008-08-07 Klipsch, Llc Ear tip
CN104230863A (zh) * 2013-06-18 2014-12-24 怀化市芬芳香料有限公司 光学活性氧化玫瑰的制备方法
CN104230862A (zh) * 2013-06-18 2014-12-24 怀化市芬芳香料有限公司 高顺式玫瑰醚的制备方法
WO2023174983A1 (en) 2022-03-17 2023-09-21 Givaudan Sa Process

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19942997A1 (de) * 1999-09-09 2001-03-15 Studiengesellschaft Kohle Mbh Verfahren zur Herstellung von Rosenoxid über Halohydrine oder Epoxide

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4429144A (en) * 1981-12-18 1984-01-31 Basf Aktiengesellschaft Preparation of rose oxide predominantly containing the Z isomer

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL276939A (enExample) * 1961-04-07
DE1443338C3 (de) * 1961-05-18 1974-02-28 Studiengesellschaft Kohle Mbh, 4330 Muelheim Verfahren zur Herstellung von cyclischen 6-Ring-Äthern
CH503723A (de) * 1966-03-30 1971-02-28 Roure Bertrand Dupont Sa Verfahren zur Herstellung von 2-(2-Methyl-1-propenyl)-4-methyl-tetrahydropyran
JP3374357B2 (ja) * 1995-08-29 2003-02-04 高砂香料工業株式会社 ３，７−ジメチル−５，７−オクタジエン−１−オールの製造方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4429144A (en) * 1981-12-18 1984-01-31 Basf Aktiengesellschaft Preparation of rose oxide predominantly containing the Z isomer

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003087387A1 (en) * 2002-04-08 2003-10-23 Council Of Scientific And Industrial Research Chemo-enzymatic synthesis of optically enriched rose-oxides
WO2006070383A1 (en) * 2004-12-27 2006-07-06 Council Of Scientific And Industrial Research Process for the preparation of nerol oxide
US20080187159A1 (en) * 2006-10-23 2008-08-07 Klipsch, Llc Ear tip
CN104230863A (zh) * 2013-06-18 2014-12-24 怀化市芬芳香料有限公司 光学活性氧化玫瑰的制备方法
CN104230862A (zh) * 2013-06-18 2014-12-24 怀化市芬芳香料有限公司 高顺式玫瑰醚的制备方法
WO2023174983A1 (en) 2022-03-17 2023-09-21 Givaudan Sa Process

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IL122108A (en) 2000-08-31
EP0842926A1 (de) 1998-05-20
IL122108A0 (en) 1998-04-05
EP0842926B1 (de) 2002-02-13
JPH10168075A (ja) 1998-06-23
DE59706373D1 (de) 2002-03-21
DE19645922A1 (de) 1998-05-14
ES2170910T3 (es) 2002-08-16

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